KR100868809B1 - Processes for producing -olefin polymer - Google Patents

Abstract

A-olefin is homopolymerized or 2 in the presence of (A) a solid catalyst component containing magnesium, titanium and halogen, (B) an organoaluminum compound having a content of 0.1% by weight or less and (C) an organozinc compound By copolymerizing at least an α-olefin, industrially advantageously, an α-olefin polymer having very high stereoregularity and excellent fluidity and having a reduced catalyst residue can be obtained industrially.

In the presence of (A) a solid catalyst component containing a titanium compound and an electron-donor, (B) an organoaluminum compound and (C) an organozinc compound, propylene is polymerized to produce crystalline polypropylene, whereby propylene and ethylene and // Alternatively, by copolymerizing an α-olefin having 4 or more carbon atoms, it is possible to efficiently produce a propylene block copolymer composed of a homopolymerized portion having high fluidity and a copolymerized portion having a high molecular weight.

Description

Process for producing α-olefin polymer {PROCESSES FOR PRODUCING α-OLEFIN POLYMER}             

The present invention relates to a method for producing an α-olefin polymer, and more particularly, to a novel method for preparing an olefin polymer that provides an olefin polymer with high stereoregularity and excellent fluidity, and propylene, ethylene and / or 4 carbon atoms. It relates to a process for producing a propylene block copolymer composed of the above α-olefins.

Olefin polymers, in particular polypropylene (hereinafter referred to as PP), are crystalline high molecular compounds, which are excellent in stiffness, tensile strength, heat resistance, chemical resistance, optical properties, processability, etc., and also have low specific gravity. It is widely used in the field of packaging materials.

As catalyst systems for polymerizing α-olefins, a number of catalysts are disclosed which consist of a solid catalyst component, an organoaluminum compound and, if desired, an electron-donating compound. The solid catalyst component contains magnesium, titanium, halogen elements and, if desired, electron-donating compounds. When producing an alpha-olefin polymer using such a catalyst system, hydrogen is generally used as a chain transfer agent. However, the addition of a large amount of hydrogen to obtain a highly fluid α-olepin polymer results in a decrease in stereoregularity or a decrease in productivity due to a decrease in monomer concentration in the polymerization field. There is this.

As mentioned above, in order to improve the fluidity of the polymer in terms of processability, it is common to increase the amount of hydrogen as a chain transfer agent at the time of polymerization. However, since the pressure resistance of the reactor is limited, the monomer concentration that can be introduced into the reactor decreases as the hydrogen concentration increases. This leads to deterioration of economic efficiency by lowering catalyst efficiency.

It is a first object of the present invention to provide a method of industrially advantageously producing an α-olefin polymer having very high stereoregularity, excellent fluidity and reduced catalyst residue in the polymer.

The propylene block copolymer (hereinafter referred to as block PP) is produced by a step of polymerizing propylene to produce a propylene homopolymer and then polymerizing the copolymer. As a characteristic required for the block PP, it has a balance excellent in mechanical properties and impact resistance inherent in the homopolypropylene. In addition, excellent moldability, appearance and elongation are required. It is known that a structure composed of a homopolymerization portion having excellent fluidity and a copolymerization portion having a relatively high molecular weight satisfies this requirement.

In order to improve the fluidity of the homopolymerization section, the amount of hydrogen generally used as a chain transfer agent in the polymerization is increased. However, when the hydrogen used in the first stage homopolymerization affects the conditions of the second stage copolymerization, that is, when it is degassed or partially degassed between the first stage polymerization and the second stage polymerization, the number of homopolymerization stages If the amount is too large, the block PP having the desired impact resistance cannot be obtained because the amount of hydrogen used in the reactor used in the second stage copolymerization increases to decrease the molecular weight of the copolymerization portion. In order to improve the impact resistance of the block PP, it is necessary to completely remove hydrogen between the first stage polymerization and the second stage polymerization, in which case facility correspondence is required. In addition, when the amount of hydrogenation added during polymerization increases, the internal pressure of the polymerization apparatus increases. However, since the internal pressure of the polymerization apparatus has a limit, the amount of hydrogenation at the time of polymerization also naturally has an upper limit. In this case, the flowability of the obtained homopolypropylene is limited and a block PP having the desired properties cannot be obtained.

Increasing the fluidity of the homopolymerization portion of the block PP by decomposing the polymer, it is not possible to obtain a fluidity suitable for the melt index (MI). Moreover, since the molecular weight of a block part also falls, problems, such as causing the fall of physical properties, such as impact resistance, arise.

Therefore, there has been a demand for a method for producing a homogeneous polymer having high fluidity without involving a decrease in the molecular weight of the copolymerization portion or an increase in the reactor internal pressure.

A second object of the present invention is to provide a method for efficiently producing a block polypropylene composed of a homopolymerization part having high fluidity and a copolymerization part having a high molecular weight.

Summary of the Invention

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the manufacturing method of the alpha olefin polymer which has the above subjects, in the 1st objective, the organic zinc compound is an essential component and the organic aluminum compound with a small content rate of a hydroaluminum compound is used. It was found that by this, the α-olefin polymer can be industrially advantageously produced.

That is, a 1st invention provides the manufacturing method of the olefin polymer shown next.

[1] α-olefins alone in the presence of (A) a solid catalyst component containing magnesium, titanium and halogen, (B) an organoaluminum compound having a content of 0.1 wt% or less and (C) an organozinc compound A method for producing an α-olefin polymer which is polymerized or copolymerizes two or more α-olefins.

[2] The method for producing the α-olefin polymer of [1], wherein the solid catalyst component of (A) further contains an electron-donor.

[3] The method for producing an alpha -olefin polymer according to the above [1] or [2], wherein the component (C) is an organic zinc compound represented by the following formula (1).

ZnR ¹ R ²

Where

R ¹ and R ² each represent a hydrocarbon group having 1 to 10 carbon atoms, which may be the same group or a different group.

[4] The method for producing the α-olefin polymer according to any one of [1] to [3], further comprising (D) an electron-donating compound.

[5] The method for producing an alpha -olefin polymer according to any one of [1] to [4], wherein the content rate of the hydroaluminum compound in the (B) organoaluminum compound is 0.01% by weight or less.

In addition, in the second aspect, when the organic zinc compound coexists in the propylene polymerization catalyst containing the titanium compound, the electron-donor and the organoaluminum compound during the first stage homopolymerization, the propylene alone has excellent molecular weight and excellent fluidity. It was found that a polymer can be obtained and that the molecular weight is not reduced in the second stage copolymerization.

According to this production method, for example, in a slurry process for dissolving propylene in an inert hydrocarbon solvent to produce a propylene polymer, or a gas phase process for producing propylene polymer by reacting propylene in a gas state, there is no need to increase the amount of hydrogen, It is possible to produce propylene homopolymers with the desired flowability under low hydrogen partial pressure conditions. When manufacturing block PP, the molecular weight of the copolymerization part of a 2nd step is not reduced. For example, in the production process of producing a propylene polymer in liquid propylene, the hydrogen pressure can be lowered, and even in a process where the pressure resistance is not high, a propylene homopolymer excellent in fluidity can be easily produced with a small amount of hydrogen.

That is, 2nd invention provides the manufacturing method of the following propylene block copolymer.                 

[1] In the presence of (A) a solid catalyst component containing a titanium compound and an electron-donor, (B) an organoaluminum compound and (C) an organozinc compound, propylene is polymerized to produce crystalline polypropylene, and then A method for producing a propylene block copolymer in which propylene is copolymerized with propylene and / or an α-olefin having 4 or more carbon atoms in the presence of crystalline polypropylene.

[2] The method for producing the propylene block copolymer according to the above [1], wherein the component (A) further comprises a magnesium compound.

[3] The method for producing a propylene block copolymer according to the above [1] or [2], wherein (D) the electron-donating compound is further present to produce a crystalline propylene block copolymer.

[4] The method for producing the propylene block copolymer according to the above [3], wherein the electron-donating compound is an organosilicon compound.

[5] The component (A) is obtained by contacting a titanium compound and a magnesium compound with each other at a temperature of 120 to 150 ° C in the presence of an electron-donor, followed by washing with an inert solvent at a temperature of 100 ° C to 150 ° C. The manufacturing method of the propylene block copolymer as described in [3] or [4].

[6] The component (A) is obtained by contacting a titanium compound and a magnesium compound with each other at a temperature of 120 to 150 ° C in the presence of an electron-donor and a silicon compound, followed by washing with an inert solvent at a temperature of 100 ° C to 150 ° C. The manufacturing method of the propylene block copolymer as described in said [5].

[7] The method for producing the propylene block copolymer according to any one of [1] to [6], wherein the component (C) is an organic zinc compound represented by the following formula (1).

Formula 1

ZnR ¹ R ²

Where

R ¹ and R ² each represent a hydrocarbon group having 1 to 10 carbon atoms, which may be the same group or a different group.

[8] The propylene block according to any one of the above [1] to [7], wherein (E) an electron-donating material is added before or during copolymerization of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms. Method of Preparation of Copolymer.

The process for producing the α-olefin polymer of the present invention (first invention and second invention) includes (A) a solid catalyst component, (B) an organoaluminum compound and (C) an organozinc compound, and (D) an electron, if necessary. In the presence of a donor compound, homopolymerization or copolymerization of the α-olefin.

In the first invention, (a) magnesium, (b) titanium and (c) halogen atoms are used as essential components in the (A) solid catalyst component, and (d) an electron-donor is used as necessary. The organoaluminum compound whose content rate of a hydroaluminum compound is 0.1 weight% or less is used for (B) organoaluminum compound.

In the second invention, (a) titanium compounds and (d) electron-donors are used as essential components in (A) solid catalyst components, and (a) magnesium compounds and (e) silicon compounds are used as necessary. Propylene is polymerized in the presence of the components to produce crystalline polypropylene. A propylene block copolymer is then prepared by copolymerizing propylene with ethylene and / or an α-olefin having 4 or more carbon atoms in the presence of the polypropylene. As the (E) electron-donating material added before or during copolymerization of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms, (d) an electron-donor or (D) an electron-donating compound is used. do.

Each component and the manufacturing method of the catalyst for olefin polymerization in this invention are described below.

(A) solid catalyst component

(a) magnesium compounds

Component (A) of the first invention should contain magnesium. Therefore, a magnesium compound is used for manufacture of (A) component.

A magnesium compound is used for component (A) of 2nd invention as needed.

There is no particular limitation on the magnesium compound. The magnesium compound represented by general formula (I) can be used preferably.                 

MgR ³ R ⁴

In the above formula, R ³ and R ⁴ represent a hydrocarbon group, an OR ⁵ group (R ⁵ is a hydrocarbon group) or a halogen atom.

Examples of the hydrocarbon group of R ³ and R ⁴ include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of OR ⁵ groups, R ⁵ may be mentioned are an alkyl group, cycloalkyl group, aryl group and aralkyl group of 1 to 12 carbon atoms. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom. R ³ and R ⁴ may be the same group or different groups.

Examples of the magnesium compound represented by the formula (I) include dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, diphenyl magnesium and dicyclohexyl magnesium. Alkyl magnesium and aryl magnesium; Alkoxymagnesium and aryloxymagnesium, such as dimethoxymagnesium, diethoxy magnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium and dicyclohexyloxymagnesium; Ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, isopropylmagnesium chloride, isobutylmagnesium chloride, t-butylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride and bromide, Alkyl magnesium halides and aryl magnesium halides such as butyl magnesium iodide; Alkoxymagnesium halides and aryloxymagnesium halides such as butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide and ethoxymagnesium iodide; Magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide.

Of these magnesium compounds, magnesium halides, alkoxymagnesiums, alkylmagnesiums and alkylmagnesium halides are preferable in view of polymerization activity and stereoregularity.

The magnesium compound may be prepared from metal magnesium, or a compound containing magnesium.

For example, the magnesium compound may be prepared by contacting metal magnesium with halogen and alcohol.

Examples of the halogen include iodine, chlorine, bromine and fluorine. Of these halogens, iodine is preferred. Examples of the alcohols include methanol, ethanol, propanol, butanol, cyclohexanol and octanol.

As another example, the magnesium compound may be prepared by contacting a halide with an alkoxymagnesium compound represented by the formula Mg (OR ⁶ ) ₂ (wherein R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms).

Examples of the halides include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride, and the like, in addition to the silicon compound (e) described later. Among these compounds, silicon tetrachloride is preferable in terms of polymerization activity and stereoregularity. Preferable examples of the hydrocarbon group represented by R ⁶ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group and octyl group; Alkenyl groups such as cyclohexyl group, allyl group, propenyl group and butenyl group; Aryl groups such as phenyl group, tolyl group and xylyl group; Aralkyl groups, such as a phenethyl group and 3-phenylpropyl group, are mentioned. Among them, an alkyl group having 1 to 10 carbon atoms is more preferable.

The magnesium compound may be supported on a carrier such as silica, alumina and polystyrene.

The said magnesium compound can be used individually or in combination of 2 or more types. It may also contain other elements, such as halogens, silicon, and aluminum, such as iodine, and may contain electron-donors, such as alcohols, ethers, and esters.

(b) titanium compounds

In 1st invention and 2nd invention, (A) component needs to contain titanium. Therefore, a titanium compound is used for manufacture of (A) component.

There is no particular limitation on the titanium compound. Titanium compounds represented by the formula (II) can be preferably used.                 

TiX ¹ _p (OR ⁷ ) _4-p

In the above formula (II), X ¹ represents a halogen atom, chlorine atom and bromine atom are preferable, and chlorine atom is more preferable. R ⁷ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear group, a branched group or a cyclic group, and may have a hetero atom such as sulfur, Y nitrogen, oxygen, silicon, and phosphorus. . Hydrocarbon groups having 1 to 10 carbon atoms are preferred, alkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups and the like are more preferred, and linear or branched alkyl groups are most preferred. If multiple -OR ⁷ groups are present, they can be the same or different from one another. Examples of the R ⁷ group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group and phenethyl group. p represents the integer of 0-4.

Examples of the titanium compound represented by Formula II include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium and tetra Tetraalkoxytitaniums such as cyclohexyloxytitanium and tetraphenoxytitanium; Titanium tetrahalide, such as titanium tetrachloride, titanium tetrabromide, and titanium iodide; Trihalogenated alkoxytitanium such as methoxytitanium trichloride, ethoxy titanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride and ethoxytitanium tribromide; Dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride and diethoxytitanium dibromide; And monohalogenated trialkoxytitaniums such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride. Among these compounds, high halogen-containing titanium compounds are preferable in terms of polymerization activity, and titanium tetrachloride is more preferable. The said titanium compound can be used individually or in combination of 2 types or more, respectively.

(c) halogen atoms

The halogen contained in the solid catalyst component of component (A) of the first invention is generally supplied from the above-described magnesium compound and titanium compound.

(d) electron-donor

Examples of the electron-donor which is an optional component of the first invention and which is an essential component of the second component include esters of alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, organic acids or inorganic acids, monoethers, diethers or polyethers. Oxygen-containing electron-donors such as ethers such as these; And nitrogen-containing electron-donors such as ammonia, amines, nitriles and isocyanates. Examples of the organic acid include carboxylic acid, specifically malonic acid.

Of these electron-donors, esters of polyhydric carboxylic acids and polyethers are preferred. More preferably, it is an ester of aromatic polyhydric carboxylic acid. Most preferred are diesters of aromatic dicarboxylic acids in terms of polymerization activity. As an organic group of an ester part, a linear, branched or cyclic aliphatic hydrocarbon group is preferable.

As an example of an aromatic dicarboxylic acid diester, the dialkyl ester of dicarboxylic acid is mentioned. Examples of dicarboxylic acids include phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6.7,8- And dicarboxylic acids such as tetrahydronaphthalene-2,3-dicarboxylic acid, indan-4,5-dicarboxylic acid and indan-5,6-dicarboxylic acid. Examples of the alkyl group of the dialkyl ester moiety include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 1-methylbutyl group and 2-methyl Butyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethyl Butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 2-ethylhexyl group And 3-ethylhexyl group, 4-ethylhexyl group, 2-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group and 3-ethylpentyl group.

Of these compounds, phthalic acid diesters are preferred. In view of activity and stereoregularity, the organic group of the ester moiety is preferably a straight or branched aliphatic hydrocarbon having 4 or more carbon atoms. Examples of the phthalic acid diester include di-n-butyl phthalate, diisobutyl phthalate and di-n-heptyl phthalate.

Examples of the polyether include compounds represented by the following general formula (III).                 

Where

n is an integer from 2 to 10,

R ⁸ to R ¹⁵ are each a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon,

R ¹¹ and R ¹² may be the same substituent or different substituents.

Any of R ⁸ to R ¹⁵ , preferably R ¹¹ and R ^12, may in common form a ring other than a benzene ring and may have atoms other than carbon in the main chain.

Examples of the polyether compound represented by Formula III include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3 Dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl)- 1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-di Cyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl- 1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxy Propane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2 -Methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2- Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diiso Butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl -1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylpart Tyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimeth Oxypropane, 2,2-dinopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3- Dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1 , 3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s- Butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-iso Propyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane , 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-di Cyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3- Bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxy Pentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2 , 4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisonepentyloxyethane, 1,3-dinopentyloxypropane, 2,2-tetramethylene-1,3 -Dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2, 8-dioxaspiro [5,5] undecane, 3,7-dioxaspiro [3,3. 1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1, 1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1-dimethoxymethylcyclo Pentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclo-hexane, 2-isobutyl-2-methoxymethyl-1,3- Dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2- Sopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1 , 3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxy-methyl) silane, cyclohexyl-t-butylbis (methoxymethyl) silane and i- And propyl-t-butylbis (methoxymethyl) silane.

Among these compounds, 1,3-diether is preferable, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy-propane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxy -Propane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane and 2-cyclopentyl-2-isopropyl-1,3 -Dimethoxypropane is more preferred.

The compounds may be used alone or in combination of two or more thereof.

(e) silicon compounds

In the present invention, the silicon compound represented by the following general formula (IV) can be used as component (e) in addition to the components (a), (b) and (d) in the preparation of the solid catalyst component, if necessary.

Si (OR ¹⁶ ) _q X ² _4-q

Where

R ¹⁶ is a hydrocarbon group,

X ² is a halogen atom,

q is an integer of 0-3.

By using a silicon compound, catalyst activity and stereoregularity can be improved and fine powder in the produced polymer can be reduced.

In formula (IV), X ² is a halogen atom. Of these, chlorine atoms and bromine atoms are preferable as halogen atoms, and chlorine atoms are particularly preferable. R ¹⁶ may be a saturated group or an unsaturated group, may be a linear group, a branched group, or a cyclic group, and may be a hydrocarbon group having hetero atoms such as sulfur atom, nitrogen atom, oxygen atom, silicon atom and phosphorus atom. Can be. Hydrocarbon groups having 1 to 10 carbon atoms are preferable, and alkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups and aralkyl groups are more preferable. If multiple -OR ¹⁶ groups are present, they can be the same or different from one another. Examples of R ¹⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group and phenethyl group. q represents the integer of 0-3.

Examples of the silicon compound represented by the formula (IV) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxycyclochlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxycyclochlorosilane , Propoxy citrichlorosilane, dipropoxydichlorosilane and tripropoxychlorosilane. Of these compounds, silicon tetrachloride is preferred. The said silicon compound can be used individually or in combination of 2 or more types.

Preparation of Solid Catalyst Components

In order to prepare the solid catalyst component (A) of the first invention, the (a) magnesium compound, (b) titanium compound, and (d) electron-donor or (e) silicon compound, if necessary, Can be contacted.

As an example of the said conventional method, the method of Unexamined-Japanese-Patent No. 78-43094, Unexamined-Japanese-Patent No. 80-135102, Unexamined-Japanese-Patent No. 80-135103, and Unexamined-Japanese-Patent No. 81-18606 is mentioned. Can be mentioned. Specific examples include the following method. (1) a method of reacting a product with a titanium compound by grinding in the presence of a magnesium compound or a complex of a magnesium compound and an electron-donor, an electron-donor and a purpose, in the presence of a grinding aid, (2) a liquid product of a magnesium compound having no reducing ability And a liquid titanium compound react with each other in the presence of an electron-donor to precipitate a solid titanium composite, (3) a method of reacting the product obtained in (1) or (2) with a titanium compound, (4) the A method of reacting the product obtained in (1) or (2) with an electron-donor and a titanium compound, (5) grinding a magnesium compound or a complex of a magnesium compound and an electron-donor according to the electron-donor, titanium compound and the purpose It may be prepared by a method of milling in the presence of an adjuvant and treating with a halogen or a halogen compound.

Further examples of preparing the solid catalyst component of the above (A) include Japanese Patent Laid-Open No. 81-166205, Japanese Patent Laid-Open No. 82-63309, Japanese Patent Laid-Open No. 82-190004, and Japanese Patent Laid-Open The method of 82-300407 and Unexamined-Japanese-Patent No. 83-47003 is mentioned. In addition, the solid catalyst component of component (A) is a composite containing one or more of oxides of elements belonging to periodic table II to IV, such as oxides such as silicon oxide and magnesium oxide or oxides of elements belonging to periodic table II to IV. Oxides such as silica-alumina-supported solids, electron-donor and titanium compounds can be prepared by contacting in a solvent at a temperature of 0 to 200 캜, preferably 10 to 150 캜 for 2 minutes to 24 hours. .

The amount of the titanium compound to be used is generally 0.5 to 100 mol, preferably 1 to 50 mol, based on 1 mol of magnesium of the magnesium compound. In addition, the amount of the electron-donor to be used is generally 0.01 to 10 moles, preferably 0.05 to 1.0 moles, per 1 mole of magnesium of the magnesium compound. In addition, silicon tetrachloride may be added as the halogen compound.

Generally this contact temperature is -20-200 degreeC, Preferably you may be 20-150 degreeC. The contact time is generally 1 minute to 24 hours, preferably 10 minutes to 6 hours. There is no particular limitation on this contact order. For example, each component can be contacted in the presence of an inert solvent such as a hydrocarbon, and can be contacted after diluting each component with an inert solvent such as a hydrocarbon in advance. Examples of the inert solvent include aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, n-octane and isooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; And mixtures of these solvents.

The titanium compound may be contacted with the other components two or more times to sufficiently support the magnesium compound serving as a catalyst carrier. The solid catalyst component obtained by contacting can be washed with an inert solvent such as hydrocarbon. Examples of the inert solvent may be the inert solvent. The solid product obtained may be stored under dry conditions or in an inert solvent such as a hydrocarbon.

In the second invention, any solid catalyst component containing (b) titanium compound and (d) electron-donor can be used as (A) solid catalyst component. The solid catalyst component comprises contacting (b) the titanium compound and (a) the magnesium compound at a temperature of 120 to 150 ° C. in the presence of (d) the electron-donor, followed by washing the product with an inert solvent at a temperature of 100 to 150 ° C. It is preferred that it is obtained by. The treatment is preferably carried out in the presence of (e) a silicon compound in combination with (d) an electron-donor. There is no particular limitation on the order of contact. For example, each component may be contacted with each other in the presence of an inert solvent such as a hydrocarbon, or may be contacted by diluting each component with an inert solvent such as a hydrocarbon in advance. Examples of inert solvents include aliphatic hydrocarbons such as n-octane, n-decane and ethylcyclohexane; Alicyclic hydrocarbons; And mixtures of these solvents.

The titanium compound is generally used in an amount of 0.5 to 100 mol, preferably 1 to 50 mol, based on 1 mol of magnesium of the magnesium compound. If the molar ratio is out of the above range, the catalyst activity may be insufficient. The electron-donor is generally used in an amount of 0.01 to 10 mol, preferably 0.05 to 1.0 mol, based on 1 mol of magnesium of the magnesium compound. If the molar ratio is out of the above range, the catalytic activity or stereoregularity may be insufficient.

The contact of each component is carried out at 120 to 150 ° C., preferably 125 to 140 ° C. after mixing all the components together. When the contact temperature is out of the above range, the effect of improving the catalytic activity and stereoregularity may not appear sufficiently. In addition, the contacting is generally carried out for 1 minute to 24 hours, preferably for 10 minutes to 6 hours. In the case of using a solvent, the pressure varies depending on the solvent and the contact temperature. The pressure is generally 0 to 5 MPaG, preferably 0 to 1 MPaG. In view of uniformity of contact and contact efficiency, it is preferable to stir the mixture while bringing each component into contact with each other.

In addition, it is preferable to sufficiently support the titanium compound on the magnesium compound which serves as a catalyst carrier by contacting it two or more times.

When a solvent is used in the operation of bringing each component into contact with each other, the solvent is generally used in an amount of 5,000 ml or less, preferably 10 to 1,000 ml, per mole of titanium compound. If the amount of the solvent is outside the above range, the uniformity of the contact and the contact efficiency may deteriorate.

It is preferable to wash the solid catalyst component obtained after the contacting with an inert solvent at a temperature of 100 to 150 캜, preferably 120 to 140 캜. If the washing temperature is out of the above range, the effect of improving the catalytic activity and stereoregularity may not appear sufficiently. Examples of inert solvents include aliphatic hydrocarbons such as n-octane and n-decane; Alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as tetrachloroethane and chlorofluoro-carbons; And mixtures of these solvents. Of these solvents, aliphatic hydrocarbons are preferred.

There is no particular limitation on the cleaning method. Methods such as decantation and filtration are preferred. There is no particular limitation on the amount of inert solvent used, the washing time, and the number of washings. For 1 mole of magnesium compound it is generally washed with 100 to 100,000 ml, preferably 1,000 to 50,000 ml, for 1 minute to 24 hours, preferably 10 minutes to 6 hours. If the conditions are out of this range, the cleaning may be insufficient.

The washing pressure varies depending on the type of solvent and the washing temperature. The pressure is generally 0 to 5 MPaG, preferably 0 to 1 MPaG. It is preferable to stir the mixture containing the solid catalyst component in terms of washing uniformity and washing efficiency in washing the solid catalyst component.                 

The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as a hydrocarbon.

(B) organoaluminum compound

There is no particular limitation on the (B) organoaluminum compound used as an essential component in the first invention and the second invention. For example, an alkyl group-containing aluminum compound represented by the following general formula (VIII) can be preferably used.

R ²⁹ _m Al (OR ³⁰ ) _n X ³ _3-nm

Where

R ²⁹ and R ³⁰ each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms,

X ³ represents a halogen atom,

m is 0 <m ≦ 3, preferably 2 or 3, most preferably 3,

n is 0 ≦ n <3, preferably 0 or 1.

Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and trioctyl aluminum; Dialkylaluminum monohalides such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and dioctylaluminum monochloride; Alkyl aluminum sesquihalide, such as ethyl aluminum sesquichloride, is mentioned. Among the organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms is preferable, and trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are more preferable. An organoaluminum compound can be used individually or in combination of 2 or more types.

In the first invention, the content of the hydroaluminum compound in the organoaluminum compound (B) is 0.1% by weight or less, preferably 0.01% by weight. When the content of the hydroaluminum compound exceeds 0.1% by weight, it is impossible to industrially advantageously produce an α-olefin polymer having excellent fluidity and a reduced catalyst residue in the polymer.

(C) organozinc compound

In the first invention and the second invention, the component (C) as an essential component is preferably an organic zinc compound represented by the following general formula (1).

Formula 1

ZnR ¹ R ²

Where

R ¹ and R ² each represent a hydrocarbon group having 1 to 10 carbon atoms, which may be the same group or a different group.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, various propyl groups, various butyl groups, various hexyl groups, and various octyl groups. Examples of the alkyl zinc compound include dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc and diisobutyl zinc. Among these alkyl zinc compounds, dimethyl zinc and diethyl zinc are preferred.

(D) electron-donating compounds

In the first and second inventions, an organosilicon compound, a nitrogen-containing compound, a phosphorus-containing compound, an oxygen-containing compound having a Si-OC bond may be used as the electron-donating compound added at the time of polymerization as necessary. have. In view of polymerization activity and stereoregularity, it is preferable to use an organosilicon compound having a Si—O—C bond.

Examples of the organosilicon compound having a Si-OC bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane and tri Ethylethoxysilane, ethylisopropyldimethoxy-silane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane , t-butylmethyldimethoxysilane, t-butylethyl-dimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyl-dimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyl- Dimethoxysilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyl-dimethoxysilane, t -Butylnonyldimethoxysilane, t-butyldecyldimethoxy-silane, t-part (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexyl-methyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl-propyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, Cyclohexyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyl-dimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane , Diphenyldimethoxysilane, phenyl-triethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl-trimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimeth Methoxysilane, t-butyltrimethoxysilane, s-butyltrimethoxy-silane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyl-trimethoxysilane, cyclohexyltrimethoxysilane, norbornane Trimethoxy-silane, Indenyl Limethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (isobutoxy) dimethoxysilane, t -Butyl (t-butoxy) dimethoxysilane, texyl trimethoxysilane, texyl isopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyl-dimethoxysilane , Texylisopropyldimethoxysilane, texylcyclopentyl-dimethoxysilane, texyl myristyl dimethoxysilane, and texylcyclohexyl-dimethoxysilane.

The organosilicon compounds may be used alone or in combination of two or more thereof.

In addition, a silicon compound represented by the following general formula (V) may be used.

Where

R ¹⁸ to R ²⁰ represent a hydrogen atom or a hydrocarbon group, which may be the same group or a different group, may combine with adjacent groups to form a ring,

R ²¹ and R ²² each represent a hydrocarbon group, which may be the same group or a different group, may combine with adjacent groups to form a ring,

R ²³ and R ²⁴ each represent an alkyl group having 1 to 20 carbon atoms, which may be the same group or a different group,

m is an integer of 2 or more,

n is an integer of 2 or more.

In the above general formula (V), R ¹⁸ to R ²⁰ include a straight chain hydrocarbon group such as a hydrogen atom, a methyl group, an ethyl group, and an n-propyl group; Branched chain hydrocarbon groups such as isopropyl group, isobutyl group, t-butyl group and texyl group; Saturated cyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; Unsaturated cyclic hydrocarbon groups, such as a phenyl group and pentamethylphenyl group, are mentioned. Among these, a hydrogen atom and a C1-C6 linear hydrocarbon group are preferable, and a hydrogen, a methyl group, and an ethyl group are more preferable.

As R <^21> and R <^22> , linear hydrocarbon groups, such as a methyl group, an ethyl group, and n-propyl group; Branched hydrocarbon groups such as isopropyl group, isobutyl group, t-butyl group and hexyl group; Saturated cyclic hydrocarbon groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group; Unsaturated cyclic hydrocarbon groups, such as a phenyl group and pentamethylphenyl group, are mentioned. These may be the same or different from each other. Of these, straight-chain hydrocarbon groups having 1 to 6 carbon atoms are preferred, and methyl and ethyl groups are more preferred.

Examples of R ²³ and R ²⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group and n- And linear or branched alkyl groups such as octyl groups. These may be the same or different from each other. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.

Examples of the silicon compound represented by the formula (V) include neopentyl-n-propyldimethoxysilane, neopentyl-n-butyldimethoxysilane, neopentyl-n-pentyldimethoxysilane, neopentyl-n-hexyldimethoxy Silane, neopentyl-n-heptyldimethoxysilane, isobutyl-n-propyldimethoxysilane, isobutyl-n-butyldimethoxysilane, isobutyl-n-pentyldimethoxysilane, isobutyl-n-hexyldimethoxy Silane, isobutyl-n-heptyldimethoxysilane, 2-cyclohexylpropyl-n-propyldimethoxysilane, 2-cyclohexylbutyl-n-propyldimethoxysilane, 2-cyclohexylpentyl-n-propyl-dimethoxy Silane, 2-cyclohexylhexyl-n-propyldimethoxysilane, 2-cyclohexylheptyl-n-propyldimethoxysilane, 2-cyclopentylpropyl-n-propyl-dimethoxysilane, 2-cyclopentylbutyl-n- Propyldimethoxysilane, 2-cyclopentylpentyl-n-propyldimethoxysilane, 2-cyclopentylhexyl-n-propyl-dimeth Cysilane, 2-cyclopentylheptyl-n-propyldimethoxysilane, isopentyl-n-propyldimethoxysilane, isopentyl-n-butyldimethoxysilane, isopentyl-n-pentyldimethoxysilane, isopentyl-hexyldimethoxy Methoxysilane, isopentyl-n-hexyldimethoxysilane, isopentyl-n-heptyldimethoxysilane, isopentyl-isobutyldimethoxysilane, isopentyl neopentyldimethoxysilane, diisopentyl-dimethoxysilane, diisopentane Heptyldimethoxysilane, diisohexyldimethoxysilane, and dicyclopentyldimethoxysilane are mentioned. Examples of preferred compounds include neopentyl-n-propyldimethoxysilane, neopentyl-n-pentyl-dimethoxysilane, isopentyl neopentyldimethoxysilane, diisopentyl-dimethoxysilane, diisoheptyldimethoxysilane, And diisohexyldimethoxysilane and dicyclopentyldimethoxysilane. More preferable examples of the compound include neopentyl-n-pentyldimethoxysilane, diisopentyl-dimethoxysilane, and dicyclopentyldimethoxysilane.

The silicon compound represented by the formula (V) can be synthesized by any method. Representative synthetic routes are as follows.

In this synthesis route, the raw compound [1] is commercially available or can be obtained by conventional alkylation or halogenation. With respect to compound [1], an organosilicon compound represented by the formula (V) can be obtained by a known Grinard reaction.

The organosilicon compounds may be used alone or in combination of two or more thereof.

Examples of nitrogen-containing compounds include 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine and N-methyl-2,2,6,6-tetramethylpiperi 2,6-disubstituted piperidine, such as dean; 2,5-disubstituted azolidines, such as 2,5-diisopropylazolidine and N-methyl-2,2,5,5-tetramethylazolidine; Substituted methylenediamines such as N, N, N ', N'-tetramethylmethylenediamine and N, N, N, N'-tetraethyl-methylenediamine; And substituted imidazolidines such as 1,3-dibenzyl-imidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Examples of phosphorus-containing compounds include triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl-n-butyl phosphite and Phosphorous acid esters such as diethylphenylphosphite.

Examples of the oxygen-containing compound include 2,6-disubstituted tetrahydrofuran such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran; Dimethoxymethane derivatives such as 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene and diphenyldimethoxymethane; The polyether as described in the said (d) electron-donor is mentioned.

As the organosilicon compound used as necessary in the second invention, an organosilicon compound of an electron-donating compound represented by the following general formula (VI) can be used.

Si (OR ²⁵ ) _q R ²⁶ _4-q

Where

R ²⁵ and R ²⁶ represent a hydrocarbon group, which may be the same group or a different group,

q represents the integer of 0-3.

In the above formula (VI), R ²⁵ and R ²⁶ are hydrocarbon groups, and as described above they may be the same group or different groups. The hydrocarbon group may be a saturated group or an unsaturated group, may be a linear group, a branched group or a cyclic group, or may include heteroatoms such as sulfur, nitrogen, oxygen, silicon and phosphorus. Hydrocarbon groups having 1 to 10 carbon atoms are preferable, and an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are more preferable. If multiple -OR ²⁵ are present, they may be the same or different from each other. Examples of R ²⁵ and R ²⁶ include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group , n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group and phenethyl group. q represents the integer of 0-3.

Examples of the organosilicon compound represented by the formula (VI) include compounds described as examples of organosilicon compounds having Si—O—C bonds.

(Method for producing α-olefin polymer)

There is no particular limitation on the amount of the catalyst component used in the first invention. The solid catalyst component of component (A) is generally used in an amount of 0.00005 to 1 millimolar per liter of the reaction volume in terms of titanium atoms. The organoaluminum compound of component (B) is generally used in an aluminum to titanium atomic ratio of 1 to 5,000, preferably 10 to 500. If this atomic ratio is out of the said range, catalyst activity may become inadequate. When using electron-donating compounds such as organosilicon compounds of component (D), the molar ratio of (D) electron-donating compound to (B) organoaluminum compound is generally 0.001 to 5.0, preferably 0.01 to 2.0, More preferably, an amount of 0.05 to 1.0 is used. If this molar ratio is out of the said range, sufficient catalyst activity and stereoregularity may not be obtained.

In the first invention, an α-olefin represented by the formula (VII) is used.

R ²⁷ -CH = CH ₂

In the above formula, R ²⁷ may be a hydrogen atom or a saturated or unsaturated hydrocarbon group.

Examples of the α-olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene And vinylcyclohexane, butadiene, isoprene and piperylene. The α-olefins may be used alone or in combination of two or more thereof. Among the α-olefins, ethylene and propylene are preferable.

In 1st invention, superposition | polymerization of an olefin is performed combining said (A) solid catalyst component with (B) organoaluminum component, (C) organozinc component, and (D) electron-donating compound as needed. The polymerization can be carried out in the gas phase or in the liquid phase. The catalyst component is brought into contact with the slurry or monomer components suspended in an inert solvent such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, n-octane, cyclohexane, toluene and xylene in a gas phase. Can be. It can also be carried out in liquid propylene.

The amount of the (C) organic zinc component used in the present invention is not particularly limited as long as it is within the range in which the effects of the present invention are exhibited.

In the first invention, according to the purpose, the prepolymerization of the olefin may be carried out first, followed by the main polymerization to obtain the desired polymerization activity, stereoregularity, and polymer powder form. In the case of prepolymerization, the (A) solid catalyst component, (B) organoaluminum compound, and (C) organozinc component and / or (D) electron-donating compound are optionally n-butane, n- In an inert solvent such as pentane, isopentane, n-hexane, n-heptane, n-octane, cyclohexane, toluene and xylene, the olefin is generally 100 ° C. or lower in the presence of a catalyst prepared by mixing at a predetermined ratio, respectively, The prepolymerization product (also referred to as prepolymerization catalyst) is preferably obtained by prepolymerization at a pressure of from about 10 MPaG to about 5 MPaG at a temperature of -10 ° C to 80 ° C. In the case of prepolymerization, hydrogen may or may not be present. As the amount to prepolymerize, 0.01-5000 g is preferable, and, as for the said (A) solid catalyst component, 0.05-1000g is more preferable.

As an example of the olefin used for prepolymerization, the olefin described as an example of the alpha olefin represented by General formula (VII) is mentioned. The olefins may be used alone or in combination of two or more thereof. Of these olefins, ethylene and propylene are preferred.

In the case of prepolymerization, the above components are mixed with each other. Immediately after mixing each component, prepolymerization may be carried out by introducing olefins, or after mixing each component, aged for 0.2 to 3 hours, and then prepolymerization may be carried out by introducing olefins.

Since an olefin polymer having high fluidity is obtained while improving polymerization activity and stereoregularity, it is preferable to carry out the polymerization of the olefin in the presence of a prepolymerization catalyst, the component (B), the component (C) and the component (D). The use ratio of the prepolymerization product, (B) component, (C) component, and (D) component in this polymerization is as follows. The prepolymerization catalyst is generally used in an amount of 0.00005 to 1 mmol per liter of the reaction volume in terms of titanium atoms in the prepolymerization catalyst. The organoaluminum compound of component (B) is generally used in an aluminum to titanium atomic ratio of 1 to 5000, preferably 1 to 300. When using an electron-donating compound such as an organosilicon compound as the component (D), the molar ratio of the (D) electron-donating compound / (B) organoaluminum compound is generally 0.001 to 5.0, preferably 0.01 to 2.0. Amount is used. If this molar ratio is out of the said range, sufficient catalyst activity and stereoregularity may not be obtained.

Component (C) has a zinc to titanium atomic ratio of generally 1 to 1,000, preferably in an amount of 10 to 500. If this atomic ratio is out of the said range, catalyst activity may become inadequate.

In the present polymerization, there is no particular limitation on the type of polymerization, and it is applicable to any of solution polymerization, slurry polymerization, gas phase polymerization and bulk polymerization. Applicable to either batch polymerization or continuous polymerization. It is also applicable to two-stage polymerization or multistage polymerization under different conditions.

The reaction conditions are as follows. There is no particular limitation on the polymerization pressure. The pressure is suitably selected in terms of polymerization activity, usually from atmospheric pressure to 8 MPaG, preferably 0.2 to 5 MPaG. The temperature is generally appropriately selected from 0 to 200 ° C, preferably 20 to 150 ° C, more preferably 40 to 100 ° C. The polymerization time depends on the polymerization temperature of the olefin used as the raw material and cannot be determined uniformly. The polymerization time is generally 5 minutes to 20 hours, preferably 10 minutes to 10 hours.

The molecular weight can also be adjusted by adding a chain transfer agent such as hydrogen. Inert gas, such as nitrogen, can be used.

In 1st invention, about the said catalyst component, (A) component, (B) component, and (D) component are mixed at a predetermined ratio, and contacted with each other. According to the objective, after performing prepolymerization, (C) component is contacted. Immediately after addition of the component (C), propylene can be introduced to carry out the main polymerization. Alternatively, after the components (A), (B) and (D) are brought into contact with each other, the mixture is aged for about 0.2 to 3 hours. According to the objective, (C) component is made to contact after prepolymerization. After adding (C) component, propylene can be introduce | transduced and this polymerization can be implemented. The catalyst component may be suspended and supplied in an olefin used as an inert solvent or raw material.

In the first aspect of the invention, the post-treatment after polymerization can be carried out according to a conventional method. In the gas phase polymerization method, the polymer powder derived from the polymerization reactor can be passed through nitrogen gas to remove olefin and the like remaining in the powder, and may be pelletized with an extruder according to the purpose. In order to completely deactivate the catalyst, small amounts of water or alcohol can be added. In the bulk polymerization process, after completion of the polymerization, the monomer can be completely separated from the polymer derived from the polymerizer and then pelletized.

Typical examples of the olefin polymers obtained according to the first invention include propylene polymers. The propylene polymer may be a propylene homopolymer or a copolymer of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms. The propylene polymer may be an irregular copolymer or a block copolymer. Examples of propylene homopolymers include very high stereoregularity, such as the [mmmm] fraction measured by ¹³ C-NMR, exceeding 95 mol%, high flowability, such as a temperature of 230 ° C., load 21.18 N, in accordance with ASTM D1238 Propylene homopolymers having a melt index measured under the conditions of 20 to 1,000 g / 10 minutes, preferably 50 to 500 g / 10 minutes.

(Method for producing propylene block copolymer)

In the second invention, in terms of polymerization activity, stereoregularity and polymer powder form, it is preferable to first prepare a prepolymerization catalyst and then carry out the main polymerization. The prepolymerization catalyst is prepared by contacting the (A) solid catalyst component and (B) organoaluminum compound, and preferably (D) electron-donating compound with olefins such as propylene, ethylene, 1-butene and 1-hexene. Can be prepared. The olefins may be used alone or in combination of two or more thereof. Prepolymerization is preferably carried out in an inert solvent such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, n-octane, cyclohexane, toluene and xylene. The prepolymerization is generally carried out at a pressure of from normal pressure to about 5 MPaG at temperatures of 80 ° C. or less, preferably −10 ° C. to 60 ° C., more preferably 0 ° C. to 50 ° C. The amount of olefin to be prepolymerized is preferably 0.05 to 50 g, more preferably 0.1 to 10 g per 1 g of the solid catalyst component (A).

In the case of prepolymerization, (A) component, (B) component, and (D) component are mixed and contacted in predetermined ratio. Immediately after mixing the component (A), the component (B) and the component (D), an olefin may be introduced to carry out the prepolymerization, and the component (A), the component (B) and the component (D) are mixed and then 0.2. After the mixture is aged for 3 hours, prepolymerization can be carried out by introducing olefins.

In the first step, propylene is homopolymerized in the presence of the obtained prepolymerization catalyst, (B) organoaluminum compound, (C) organic zinc compound, and preferably (D) electron-donating compound. In a second step, the comonomer component may be introduced to effect copolymerization of propylene and comonomers. In this way, a block PP can be obtained. In the first stage homopolymerization, the melt index measured at a temperature of 230 ° C. and a load of 21.2 N (2.16 kgf) in accordance with ASTM D1238 is from 20 to 1,000 g / 10 minutes, preferably from 50 to 500 g / 10 minutes. A propylene homopolymer having can be obtained.

The comonomer is at least one of ethylene and an α-olefin having 4 or more carbon atoms. Examples of α-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. The α-olefins may be used alone or in combination of two or more thereof.                 

In the second invention, the intrinsic viscosity of the homopolymerized portion (propylene homopolymer) measured in decalin at 135 ° C is preferably 0.5 to 1.5 dl / g from the viewpoint of obtaining sufficient fluidity, and 0.5 to 1.2 dl / g is More preferred. As for the intrinsic viscosity of a copolymerization part, 1.0-10 dl / g is preferable from a viewpoint that impact resistance is not impaired, 1.5-10 dl / g is especially preferable.

Homopolymerization of propylene can be carried out in several portions depending on the purpose. When changing conditions in copolymerization, degassing operation can be performed as needed and the reaction monomer component ratio and hydrogen amount can be changed. In the preparation of block PP, the addition of an electron-donating material, since the addition of the (E) electron-donating material before or during the copolymerization with the comonomer substantially eliminates the decrease in molecular weight due to the addition of the organozinc compound. It is desirable to. As the (E) electron-donating material, the compounds exemplified as (b) electron-donor and (D) electron-donating compound can be used. Of these compounds, alcohols are preferred, and ethanol is more preferred. In this case, the addition amount of the (E) electron-donating material is preferably about 0.01 to 1.5 moles with respect to 1 mole of the total amount of the (B) organoaluminum compound and (C) organozinc compound used in the propylene homopolymerization. Do. When the addition amount of an electron-donating substance exceeds 1.5 mol, the activity of a catalyst may fall too much.

The polymerization can be carried out in the gas phase or in the liquid phase. In addition, the polymerization is carried out in a slurry state in which a prepolymerization catalyst is suspended in an inert solvent such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, n-octane, cyclohexane, toluene and xylene, for example. It can be carried out by contacting the monomer or by contacting the monomer component with the catalyst in the gas phase. Moreover, superposition | polymerization can also be performed in liquid propylene. It is applicable to either batch polymerization or continuous polymerization, and also to two-stage polymerization or multistage polymerization under different conditions.

There is no particular limitation on the amount of the catalyst component used in the second invention. The solid catalyst component of component (A) is generally used in an amount of 0.00005 to 1 millimolar per liter of the reaction volume in terms of titanium atoms. The organoaluminum compound of component (B) is generally used in an aluminum to titanium atomic ratio of 1 to 1,000, preferably 10 to 500. If this atomic ratio is out of the said range, catalyst activity may become inadequate. In addition, the organozinc compound of component (C) has an aluminum to zinc atomic ratio of generally 1 to 10,000, preferably 1 to 1,000, more preferably 1 to 500. If this atomic ratio is less than 1, the addition effect of (C) component may not appear. If the atomic ratio exceeds 10,000, the catalytic activity may be insufficient. The molar ratio of the (D) electron-donating compound to the (B) organoaluminum compound is generally used in an amount of 0.001 to 5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0. If this molar ratio is out of the said range, sufficient catalyst activity and stereoregularity may not be obtained. However, when prepolymerization is carried out, the molar ratio of component (D) to component (B) can be further reduced.

The reaction conditions are as follows. There is no particular limitation on the pressure. In view of the polymerization activity, the polymerization pressure is generally from atmospheric pressure to 10 MPaG, and the polymerization temperature is generally appropriately selected from -80 to 180 캜, preferably 20 to 150 캜.

In the second invention, the post-treatment after polymerization can be carried out according to a conventional method. That is, in the gas phase polymerization method, nitrogen gas can be passed through the polymer powder derived from the polymerization reactor to remove olefin and the like remaining in the powder, and can be pelletized by an extruder according to the purpose. Small amounts of water or alcohol can be added to completely deactivate the catalyst. After the polymerization is completed in the bulk polymerization method, the monomer can be completely separated from the polymer derived from the polymerization reactor and then pelletized.

The invention is described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

In Examples 1 to 6 and Comparative Examples 1 to 3 of the first invention, the respective physical properties and analytical values were obtained according to the following methods.

(1) Intrinsic viscosity [η]: The monomer was dissolved in decalin and measured at 135 ° C.

(2) Melt Flow Rate (MFR): Measured at 230 ° C. and a load of 21.18 N in accordance with ASTM D1238.

(3) Stereoregularity (pentad fraction (mmmm)): The polymer was dissolved in a 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene. Methyl groups measured by the method of complete decoupling of proton at 130 ° C. using ¹³ C-NMR (manufactured by NIPPON DENSHI CO., Ltd .; LA-500). Quantification using the signal. The isotactic (mmmm) pentad fraction used in the present invention is a. Sleep Valley (A.Zambelli) means the literature [Macromolecules, 6, 925 (1973 )] isotactic pentad fraction of a pentad unit in the polypropylene molecular swaejung measured by ¹³ C nuclear magnetic resonance spectrum proposed in such as do. The attribution of peaks in the measurement of ¹³ C nuclear magnetic resonance spectra was in accordance with the attribution proposed in A. Zambelly et al., Macromolecules, 8,687 (1975).

(4) Aluminum hydride content in the organoaluminum compound: The gas generated by hydrolyzing the organoaluminum compound was analyzed by gas chromatography.

In the first embodiment, the following three types of organoaluminum compounds were used.

Triethylaluminum A: aluminum hydride content 0.6% by weight

Triethylaluminum B: 0.05 wt% aluminum hydride content

Triethylaluminum C: 0.004% by weight of aluminum hydride

Commercially available triethylaluminum was distilled off, and the triethylaluminum obtained before and after distillation was adjusted by mixing aluminum hydride content as needed.

In Examples 7 to 11 and Comparative Examples 4 and 5 of the second invention, the ethylene content in the intrinsic viscosity [η], the p-xylene soluble amount and the p-xylene soluble part was determined as follows.

(1) Intrinsic viscosity [η]: The homopolymerized portion or the p-xylene soluble portion was dissolved in decalin and measured at 135 ° C.

(2) Availability of p-xylene: The amount of soluble component (W) of p-xylene at 25 ° C was determined according to the following method.

Samples of block copolymers of propylene and ethylene were quantified in 5 ± 0.05 g and placed in 1000 ml eggplant flasks. After 1 ± 0.05 g of BHT (antioxidant) is added, the rotor and 700 ± 10 ml of p-xylene are placed in a flask and a chiller is fitted to a branched flask. While operating the rotor, the flask is heated for 120 ± 30 minutes in an oil bath at 140 ± 5 ° C. to dissolve the sample in p-xylene. The contents of the flask are poured into a 1000 ml beaker and the solution in the beaker is cooled with stirring in a stirrer. Allow to cool (more than 8 hours) until the contents of the beaker reach room temperature (25 ° C.) and remove the precipitate with a wire mesh. The filtrate was filtered again and filtered and poured into 2000 ml of methanol contained in a 3000 ml beaker. It is left to stand for 2 hours or more with stirring in a stirrer. The precipitate was separated with a wire mesh and dried in air for at least 5 hours and then dried in a vacuum dryer at 100 ± 5 ° C. for 240-270 minutes to recover the soluble portion in p-xylene.

Content (Wg) of the soluble part in p-xylene in a sample is computed as W (weight%) = 100 * C / A, when a sample weight is Ag and the soluble part in p-xylene collect | recovered is Cg.

(3) ethylene content in p-xylene solubles

The ethylene unit content in the soluble part in p-xylene was measured as follows using the ¹³ C-NMR measurement method.

The soluble portion of p-xylene was evaluated according to ¹³ C-NMR measurement and the area intensities I (Tδδ), I (Tβδ), I (T (δδ), I (Tβδ), I ( Sγδ), I (Sδδ), I (Tββ), I (Sβδ) and I (Sββ) were obtained. Using these area intensities, the fractions F _EEE , f _EPE , f _PPE , f _PPP , f _PEE and f _PEP of the EEE, EPE, PPE, PPP, PEE, and PEPtriad continuous distributions were respectively calculated by the following equations:

f _EEE = [I (Sδδ) / 2 + I (Sγδ) / 4] / T

f _EPE = I (Tδδ) / T

f _PPE = I (Tβδ) / T

f _PPP = I (Tββ) / T

f _PEE = I (Sβδ) / T

f _PEP = I (Sββ) / T

Where T is I (Sδδ) / 2 + I (Sγδ) / 4 + I (Tδδ) + I (Tβδ) + I (Tββ) + I (Sβδ) + I (Sββ).

Ethylene unit content (mol%) was computed by the following formula using the fraction obtained by said formula:

Ethylene Unit Content (mol%) = 100 {f _EEE + 2 (f _PEE + f _EPE ) / 3 + (f _PEP + f _PPE ) / 3}

Finally, the ethylene unit content (% by weight) was calculated by the following equation:

Ethylene unit content (% by weight) = [28 Et (mol%) / {28 Et (mol%) + 42 (100-Et (mol%))}] × 100

In the above formula, the ethylene unit content (mol%) is Et (mol%).                 

¹³ C-NME measurement was carried out by dissolving the soluble part of p-xylene in a 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene, and using ¹³ C-NMR (Nippon Density Company Limited; LA-500) was carried out by proton complete decoupling at 130 ° C.

Example 1

(1) Preparation of Solid Catalyst Components

After filling a three-necked flask equipped with a 0.5 liter stirrer with nitrogen gas, 60 ml of dehydrated n-octane and 16 g of diethoxy magnesium were placed in the flask. The resulting mixture was heated to 40 ° C. and 2.4 mL of silicon tetrachloride was added. After stirring for 20 minutes, 1.6 ml of di-n-butyl phthalate was added. The resulting solution was heated to 80 ° C. and 77 mL of titanium tetrachloride was added dropwise. The temperature in the flask was raised to 125 ° C. and stirred for 2 hours to effect contact operation. After stirring was stopped, the solid material precipitated to remove the supernatant. 100 ml of dehydrated n-octane was added. The resulting mixture was heated with stirring to 125 ° C. and maintained at this condition for 1 minute. After the stirring was stopped, the solid material was allowed to settle and the supernatant was removed. This wash operation was repeated seven times. Then 122 ml of titanium tetrachloride were added. The temperature in the flask was raised to 125 ° C., and a second contact operation was performed. Then, washing with the dehydrated n-octane was repeated 6 times to obtain a solid catalyst component.

(2) Preparation of Prepolymerization Product

After filling a three-necked flask equipped with a 0.5 liter agitator with a nitrogen gas, the solid catalyst component was added in a dehydrated n-octane slurry so that the mass of the solid was 12 g, and the temperature was maintained at 25 ° C. 1.5 g of triethylaluminum B were added and stirred for 15 minutes, followed by 1.1 g of dicyclopentyldimethoxysilane. The solution was heated to 50 ° C. and propylene gas was introduced at a rate of 50 ml / min for 2 hours. The introduction of propylene gas was then stopped and the temperature was slowly lowered to 25 ° C. over 40 minutes. After the stirring was stopped, the solid material was allowed to settle and the supernatant was removed. Then, 100 ml of dehydrated n-octane was added and the solution was stirred for 1 minute. After the stirring was stopped, the solid material was allowed to settle and the supernatant was removed. This washing operation was repeated five times to obtain a prepolymerized product.

(3) polymerization

In a stainless steel autoclave equipped with an input tube and a stirrer, 30 g of homopolypropylene (intrinsic viscosity: 0.96 dl / g) was added as a seed powder. After drying inside the autoclave sufficiently under reduced pressure, the internal temperature was heated up to 80 degreeC, stirring. Hydrogen was introduced to adjust the hydrogen partial pressure to 0.6 MPa. Propylene was then introduced to adjust the voltage to 2.8 MPaG. 7.6 ml of triethylaluminum B (aluminum hydride content: 0.05% by weight), 0.5 ml of diethylzinc and 20 ml of dehydrated n-heptane were placed in an input tube. These materials were then introduced into the autoclave by the pressure difference between the input tube and the autoclave. 20 ml of dehydrated n-heptane, 0.4 mmol of triethylaluminum B, 1.0 mmol of dicyclopentyldimethoxysilane and 0.02 mmol of the prepolymerization product were added to titanium in the input tube. These materials were then introduced into the autoclave by the pressure difference between the input tube and the autoclave. The polymerization was carried out for 1 hour while further introducing propylene to keep the voltage constant. The temperature was then lowered and depressurized. The product was taken out and dried in vacuo to yield a propylene polymer. The results obtained are shown in Table 1.

Example 2

It carried out similarly to Example 1 except having used 1.0 mmol of diethyl zinc in Example 1. The results are shown in Table 1.

Example 3

The same procedure as in Example 1 was carried out except that triethylaluminum C (aluminum hydride content: 0.004 wt%) was used in Example 1. The results are shown in Table 1.

Example 4

The same procedure as in Example 3 was carried out except that 1.0 mmol of diethyl zinc was used in Example 3. The results are shown in Table 1.

Comparative Example 1

The same procedure as in Example 1 was conducted except that triethylaluminum A (aluminum hydride content: 0.6 wt%) was used in Example 1. The results are shown in Table 1.

Although the same amount of diethyl zinc was used in Examples 1, 3 and Comparative Example 1, the MFR, which is an indicator of fluidity, was different. In Comparative Example 1, sufficient fluidity could not be obtained as compared with Examples 1 and 3. As shown by the result of Comparative Example 2, when the amount of diethyl zinc of Comparative Example 1 was doubled, fluidity equivalent to those of Examples 1 and 3 can be obtained. However, it is thought that the amount of zinc residue contained in the polymer is higher than that of Examples 1 and 3. Accordingly, it can be seen that the methods of Examples 1 and 3 are excellent in terms of both reducing the amount of zinc residue in the polymer and excellent fluidity.

Comparative Example 2

The same procedure as in Comparative Example 1 was carried out except that 1.0 mmol of diethyl zinc was used in Comparative Example 1. The results are shown in Table 1.

In Examples 2, 4 and Comparative Example 2, the same amount of diethyl zinc was used, but the MFR, which is an indicator of fluidity, was different. In Comparative Example 2, sufficient fluidity was not obtained in comparison with Examples 2 and 4.

Example 5

The internal volume 1L stainless steel autoclave equipped with an input tube and a stirrer was sufficiently dried, and 360 ml of n-heptane, 2 mmol of triethylaluminum B, 1 mmol of diethylzinc and 0.25 mmol of dicyclopentyldimethoxysilane were added. Put in. The temperature was raised to 80 ° C., and hydrogen was introduced so that the hydrogen partial pressure was 0.2 MPa. Propylene was then introduced to adjust the voltage to 0.8 MPaG. Into an input tube, 20 ml of dehydrated n-heptane and 0.02 mmol of the prepolymerized product in terms of titanium were added. These materials were introduced by the pressure difference between the input tube and the autoclave. The polymerization was carried out for 1 hour with the addition of propylene to keep the voltage constant. 20 ml of methanol was introduced from the input tube to stop the polymerization. The temperature was then lowered and depressurized. The contents were taken out from 2 liters of methanol, filtered and dried in vacuo to afford a polymer. The results are shown in Table 1.

Example 6

In Example 5, it carried out similarly to Example 5 except having used triethyl aluminum C (aluminum hydride content: 0.004 weight%). The results are shown in Table 1.

Comparative Example 3

In Example 5, it carried out similarly to Example 5 except having used triethyl aluminum A (aluminum hydride content: 0.6 weight%). The results are shown in Table 1.

Although the usage-amount of diethyl zinc is the same amount in Example 5, 6 and Comparative Example 3, intrinsic viscosity which is an index of the molecular weight of a polymer differs. In comparison with Examples 5 and 6, in Comparative Example 3, sufficient fluidity could not be obtained because the value of the intrinsic viscosity was large and the molecular weight was large.                 

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Aluminum hydride content (% by weight) 0.05 0.05 0.004 0.004 0.05 0.004 0.6 0.6 0.6 Diethyl Zinc Usage (mmol) 0.5 1.0 0.5 1.0 1.0 1.0 0.5 1.0 1.0 Yield (g) 570 590 670 640 57 68 680 830 51 Intrinsic viscosity (㎗ / g) 1.04 0.91 1.00 0.89 0.59 0.55 1.11 1.03 1.67 MFR (g / 10 min) 93 142 85 143 60 86 Stereoregularity (mmmm) (mol%) 98.2 98.3 98.2 98.2 98.2 98.4 98.1 98.4 98.1

Example 7

Into a stainless steel autoclave equipped with a 5 liter inlet tube and a stirrer, 30 g of homopolypropylene was added as seed powder. After drying sufficiently under reduced pressure, the autoclave internal temperature was heated up to 80 degreeC. Hydrogen and propylene were introduced so that the hydrogen partial pressure was 0.6 MPaG, and the voltage was adjusted to 2.8 MPaG. 20 ml of dehydrated n-heptane, 3.6 mmol of triethylaluminum and 1.0 mmol of diethyl zinc were placed in an input tube. Then, these materials were introduced into the autoclave by the pressure difference between the input tube and the autoclave. 20 ml of dehydrated n-heptane, 0.4 mmol of triethylaluminum, 1.0 mmol of dicyclopentyldimethoxysilane, and 0.02 mmol in terms of titanium were placed in an input tube. Then, these materials were introduced into the autoclave by the pressure difference between the input tube and the autoclave. The polymerization was carried out for 1 hour while further introducing propylene to keep the voltage constant (first stage polymerization). The temperature was lowered, depressurized and a small amount of product was withdrawn. The inside of the autoclave was reduced and heated to 60 ° C. Hydrogen was added to adjust the pressure to 0.1 MPaG. A mixed gas having a molar ratio of ethylene to propylene of 3.5: 6.5 was introduced and the voltage was adjusted to 1.5 MPaG. The polymerization was carried out for 45 minutes (two stage polymerization). The temperature was lowered and depressurized. The product was taken out and dried in vacuo to afford a propylene block copolymer. The results obtained are shown in Table 2.

Example 8

Example 7 was carried out in the same manner as in Example 7, except that 6.0 mmol of diethyl zinc was used. The results are shown in Table 2.

Comparative Example 4

In Example 7, it carried out similarly to Example 7, except not using diethyl zinc. The results are shown in Table 2.

Example 9

In Example 7, the same process as in Example 7 was carried out except that no hydrogen was introduced during the second stage of polymerization. The results are shown in Table 2.

Example 10

In Example 8, it carried out similarly to Example 8 except not introducing hydrogen at the time of the superposition | polymerization of a 2nd step. The results are shown in Table 2.

Example 11

In Example 9, the same procedure as in Example 9 was carried out except that 1.0 mmol of ethanol was added at the start of the second stage of polymerization. The results are shown in Table 2.                 

Comparative Example 5

The same procedure as in Example 9 was carried out except that diethylzinc was not used in Example 9. The results are shown in Table 2.

Example 7 Example 8 Comparative Example 4 Example 9 Example 10 Example 11 Comparative Example 5 Diethyl Zinc Usage (mmol) 1.0 6.0 0.0 1.0 6.0 1.0 0.0 Active (tg / g-titanium) 810 820 680 1050 1150 780 790 Intrinsic Viscosity of Homopolymerized Part (㎗ / g) 1.04 0.90 1.17 1.00 0.94 1.01 1.24 (soluble part in p-xylene) Intrinsic viscosity (㎗ / g) 2.35 2.18 2.80 4.17 4.09 5.72 5.68 Available amount (% by weight) 18.4 18.1 18.3 18.6 14.8 12.6 15.3 Ethylene Unit Content (wt%) 29.0 29.7 29.7 30.5 27.4 31.4 28.7

According to the first invention of the present invention, an α-olefin polymer having very high stereoregularity, excellent fluidity, and reduced catalyst residue can be industrially advantageously obtained.

Further, according to the second invention, a propylene block copolymer composed of a homopolymerization part having high fluidity and a copolymerization part having a high molecular weight can be efficiently produced.

Claims (18)

(A) Magnesium compound represented by the following formula (I), titanium compound represented by the following formula (II) and a solid catalyst component containing a halogen, (B) a hydro aluminum compound containing a content of 0.1% by weight or less of formula R ²⁹ _m Al (OR ³⁰ ) _n X ³ An alkyl group-containing organoaluminum compound represented by _3-nm (R ²⁹ and R ³⁰ each represent an alkyl group having 1 to 8 carbon atoms, X ³ represents a halogen atom, m is 0 <m ≦ 3, n Is 0 ≦ ⁿ <3), and (C) an organic zinc compound represented by the formula ZnR ¹ R ² (R ¹ and R ² each represent a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different). In the presence, a method for producing an α-olefin polymer, characterized in that the α-olefin is homopolymerized or two or more α-olefins are copolymerized. [Formula I] MgR ³ R ⁴ (R ³ and R ⁴ each represent a hydrocarbon group, an OR ⁵ group (R ⁵ is a hydrocarbon group) or a halogen atom.) [Formula II] TiX ¹ _p (OR ⁷ ) _4-p (X ¹ represents a halogen atom, R ⁷ is a hydrocarbon group, p is an integer from 0 to 4.) The method of claim 1, A process for producing an α-olefin polymer further containing an electron-donor as the solid catalyst component of (A). The method of claim 2, A method of making an α-olefin polymer wherein the electron donor is an oxygen-containing electron-donor or a nitrogen-containing electron-donor. The method of claim 3, wherein A method for producing an α-olefin polymer wherein the oxygen-containing electron-donor is an alcohol, a phenol, a ketone, an aldehyde, an ester or an ether. The method of claim 4, wherein The manufacturing method of the alpha olefin polymer whose ester is malonic ester and aromatic dicarboxylic acid ester. The method of claim 4, wherein A method for producing an α-olefin polymer wherein ethers are compounds represented by the following general formula (III). [Formula III]

(n is an integer from 2 to 10, R ⁸ to R ¹⁵ are each a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, R ¹¹ and R ¹² may be the same as or different from each other, Any of R ⁸ to R ¹⁵ may commonly form a ring other than the benzene ring, and may have atoms other than carbon in the main chain.) The method of claim 1, The manufacturing method of the alpha-olefin polymer which further contains the silicon compound represented by following formula (IV) as a solid catalyst component of (A). [Formula IV] Si (OR ¹⁶ ) _q X ² _4-q (R ¹⁶ is a hydrocarbon group, X ² is a halogen atom, q is an integer from 0 to 3.) delete The method according to any one of claims 1 to 7, (D) A process for producing an α-olefin polymer having an electron-donating compound present. delete The method of claim 9, (D) The manufacturing method of the alpha-olefin polymer whose component is the organosilicon compound which has a Si-O-C bond, or the silicon compound represented by following formula (V). [Formula V]

(Wherein R ¹⁸ to R ²⁰ each represent a hydrogen atom or a hydrocarbon group, which may be the same or different from each other, may combine with an adjacent group to form a ring, R ²¹ and R ²² each represent a hydrocarbon group, which may be the same or different from each other, may combine with an adjacent group to form a ring, R ²³ and R ²⁴ each represent an alkyl group having 1 to 20 carbon atoms, which may be the same or different from each other, m is an integer of 2 or more, n is an integer of 2 or more.) delete The method according to any one of claims 1 to 7, (B) The manufacturing method of the alpha-olefin polymer whose content rate of the hydroaluminum compound in an organoaluminum compound is 0.01 weight% or less. delete The method of claim 9, (B) The manufacturing method of the alpha-olefin polymer whose content rate of the hydroaluminum compound in an organoaluminum compound is 0.01 weight% or less. delete The method of claim 11, (B) The manufacturing method of the alpha-olefin polymer whose content rate of the hydroaluminum compound in an organoaluminum compound is 0.01 weight% or less. delete